DE2711694A1 - PROCESS FOR IMPROVING THE PERFORMANCE OF ELECTROCHEMICAL SYSTEMS, ELECTROCHEMICAL CELL AND BATTERY WORKING IN ACCORDANCE WITH THIS PROCESS AND LIQUID COMPLEX USED FOR IT - Google Patents

Description

Cambridge, Massachusetts 02138, V. St. A.

Process to improve the ability to tune electrochemical systems, electrochemical cell and battery working according to this process νν \ ά daHir verwe ^ K ^ i-er flü-S j f. Pt Komnl ex

The invention relates to compounds which are used to form halogen complexes are usable, and in particular compounds that are used as an electrolyte additive for electrochemical Cells and batteries in which a halogen is considered electrochemical active agent is used.

Voltaic cells, which are an aqueous solution of zinc or Cadmium halide as an electrolyte are included although known, they are often due to a relative

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771169A • 13.

characterized by a high rate of self-discharge, a low capacitance and a high internal resistance. As elemental halogen in the aqueous electrolyte is soluble, it is difficult to separate metallic zinc or cadmium and elemental halogen to maintain and at the same time to create a system in which an acceptable percentage of the theoretical Energy storage capacity can be realized.

Various attempts have recently been made to prevent elemental halogen from migrating to the zinc or cadmium electrode. For example US Pat. No. 3,352,720 describes the use of water-insoluble, polymeric amine-llalogen complexes in place of the elemental halogen. These known structures work as halogen cells because of their poor stability However, the polyhalogens used still lack optimal capacities and self-discharge speeds.

U.S. Patent 3,816,177 describes the use of soluble quaternary ammonium halides and the like disclosed in U.S. Patent No. 3,816,177 the electrolyte can be dissolved together with a water-soluble depolarizer. When elemental halogen is released into the electrolyte, it combines with the quaternary halide to form a quaternary Polyhalide, which complexes with the depolarizer and forms an insoluble, halogen-rich, oil-poor

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term complex forms. When an inert electrode, which consists of a material that absorbs the insoluble When the complex is absorbed, an improved cell is created because the complex is relatively stable and there are the halogen molecules around the current collector are concentrated around, are available to a greater extent for the electrochemical reaction.

A further improvement in the electrochemical halogen cells has already been proposed in US patent application SN 652. The structure proposed in this application is a new electrode which contains a current-collecting base material which has incorporated into its structure an extremely stable polymer-containing quaternary ammonium, phosphonium or sulfonium sites. Since the polymer is formed in the presence of a porous current collecting base material with a large surface area, the electrodes are able to store halogons in a non-chemically active, nbor o] cVt smell'-mi ri h -, rather active state in such a way that that uniform, intimate electrical contact is maintained between the halogen-rich sites of the polymer and the current collector and that interaction between the halide in the electrolyte and the quaternary sites is greatly facilitated.

The invention provides a further improvement in the field of halogen cells and provides a large number of compounds, each of which is the electrolyte of the

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? 711694 • rf / ·

Halogen cells of the type described can be added. The compounds of the invention eliminate the need for a dipole riser or custom made electrode while still providing greater halogen complexing ability and increasing the shelf life and capacity of the cells and batteries in which they are used.

In general, the invention provides compounds which can be used as additives to the electrolyte of analog cells and batteries for halogen complex formation. The addition is selected from the group consisting of compounds with the following structural formula:

Linear (RXR * O _n ZZ (-RX-R'-) _n Z * Z ^l (-RXR ^t -) _n Z (-RX-R'-) _n , Z (-RX-R'-) _n "Z ^l

ZK-RX-R'-) Z '1, and η m

Cyc Lisch [(-RXR ¹ -) Z]

where RiIt: R can be R ¹ , Z can be Z ¹ , R and R 'are aliphatic groups containing 1 to 8 carbon atoms, n, n ¹ and n''are numbers from 1 to 100,

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m is a number from 1 to 6, Z and Z 'are selected from the large number of groups that make the halogen complex of the additive non-crystalline at 30 C, and X is an oxygen atom, HC-OR' ¹ or R ''' -C-OR ", where P" and R ¹ ' ^{1 are} aliphatic groups containing 1 to 6 carbon atoms. Z and Z ¹ can be, for example, alkyls, amides, carbocycles, carboxylates, halogenated hydrocarbons, halides, hydrogen, phosphonates, siloxanes, sulfonates, sulfones and sultones. Z and Z 'can also be selected from the functional constituents which form complexes with halogen, such as, for example, ammonium, ammonium hydrohalides, amididines, amine oxides, betaines, esters, hydroxyls, nitriles, phosphobetaines, phosphoniums, pyridiniums, pyridyls, quaternary ammonium, quaternary O-alkylhydroxylammonium , Sulfobetaines, sulfoniums, sydnones, tertiary amines, tertiary amine hydrohalides, and combinations thereof. The compounds according to the invention, when combined with one or more molar equivalents of halogen, form a halogen-rich liquid which is essentially insoluble in aqueous metal halide solutions at 30 ° C. and which can be used, if necessary, to operate certain fuel cells.

The invention thus provides a halogen complex-forming ether which can be used as an electrolyte additive for cells and Batteries of the type described can be used and by complexing elemental halogen in the electrolyte is able to improve the performance of electro-

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mix systems in which halogen is used to improve greatly.

Furthermore, the invention creates a large number of connections, any of which can be added to zinc or cadmium halide electrolytes to make halogens more effective than the above-mentioned amine haloene polymeric complexes and to complex and hold the quaternary ammonium polyhalide depolarizer systems and thereby increasing the storable Lt and the self-discharge the primary and secondary cells and batteries in which the complex formation connection is used, to reduce.

The invention further provides a compound which is capable of forming halogen complexes in an electrochemical cell or to create battery that eliminates the need of adding a depolarizer to the electrochemical System eliminated.

The invention also provides compounds which, when combined with one or more molar equivalents of halogen for every oxygen atom in the compounds are complexed, form insoluble liquids in aqueous metal halide solutions when kept at 30 C, and which are excreted from the aqueous electrolyte to provide a source of halogen to be contained in a halogen cell or battery can be used.

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The invention further provides compounds which, when combined with one or more molar equivalents of halogen are complexed and kept below 30 C, form suitable conductive liquids and therefore the Halogens allow them to stick to the electrode of a halogen cell or battery at a reasonable rate to experience an electrochemical reduction.

The invention further provides a large number of compounds which do not form crystalline zincates when they are placed in aqueous zinc halide solutions.

Finally, the invention provides compounds which, when complexed with one or more molar equivalents of halogen for each oxygen atom in the compounds, form liquids that can be pumped at 30 C and stored indefinitely, making them suitable for use in a regenerative fuel cell or Batteries are suitable for storing bromine and do not alter the carbon electrodes or most plastics that can be attacked by halogen.

Several embodiments of the invention are described below with reference to the accompanying drawings described in more detail. Show it:

Fig. 1 is a cross-sectional view of a cell,

in which the complexing compounds according to the invention can be used

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are,

Fig. 2 in a diagram, the voltage, up

carry over ampere hours per square meter of electrode surface, which the shows improved storage capacity of cells constructed according to FIG. 1, when a complexing compound according to the invention is added to the electrolyte is,

Fig. 3 is a schematic representation of a re

Generative fuel cell with a circulating electrolyte in which the complexing compounds can be used according to the invention, and

4 is a cross-sectional view of a battery;

in which the complexing compounds according to the invention can be used.

First , some terms that are used in the description and in the claims will be explained. For example, the terms "zinc electrode" and "bromine electrode" do not mean that the electrodes are made exclusively from these materials. As is customary in practice, these terms are only used to indicate the electrochemically active, reactive element. The metal and halogen electrodes of the cells, in which

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When the compounds of the invention are used, they are electrochemically conductive and are preferred porous. Carbon in its various forms is a preferred material. The carbon of the metal electrode serves as an application surface for the reactive metal.

Further, although reference is made to a counter electrode and a metal electrode, it will be understood that the connections can be used according to the invention in cells which contain more than one pair of electrodes, and in batteries, which are made up of two or more cells in a known manner. Since cadmium is electrochemically similar to zinc is, it is also clear that the zinc of the electrode and the electrolyte can be replaced by cadmium. Although bromine is used throughout the specification and claims, it is clear that chlorine, Iodine or any combination of bromine, chlorine and iodine can be substituted. Although on the addition of an ether additive Referring to it, a compatible mixture of ether supplements can be used in each cell.

The following partial reactions occur during the discharge of the known zinc-bromine cell:

at the cathode Br ~ + 2e ~ + - 2Br "

at the anode Zn ° * · Ζη ^π + 2e

When charging, the reactions are reversed:

at the cathode 2Br "» · Br ₉ + 2e

at the anode Zn + 2e ~ · - Zn °

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-W-

The citric bromide of the electrolyte is thus during the Charge consumed and generated while discharging. For the cell to work properly, the Br, which apparently must be near the cathode when the Cell is discharged, stored somewhere. Since Br in Water, which contains dissolved metal halides, is soluble, precautions must be taken to keep it in mind to prevent wandering through the watery ^ lektrolvt ^ n? u and react directly with the metallic zinc on the anode. This goal has been achieved by using a porous, conductive base material, preferably made of carbon, of those described in US Pat. No. 3,816,177 Type and one or more of the compounds have been incorporated into an otherwise conventional halogen cell. When the electrolyte has been absorbed by the porous electrode with the ether according to the invention, during The bromine generated by the charge is complexed by the ether and prevented from being in the aqueous electrolyte to be solved.

It is known that ethers can form a complex with halogens (see, for example, ZA-PS 68/8126). According to the Invention it has been found that some ethers or polyethers are quite effective stores for the above indicated halogens and in particular for bromine in an electrochemically active, but not chemically active state and that the performance of the halogen cells and halogen batteries is considerably improved can if such connections the conventional

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Zinc or cadmium halide electrolytes can be added.

The complex forming compounds according to the invention are substances which have the following structural formula:

Linear

(R-X-R ') Z on

2 (-RXR ¹ -) Z ¹ η

) Z (-RX-R'-), Z (-RXR · -) η η _η ··

Z [(- RX-R'-) Z '), and η m

Cyclically
-X-R'-) Z]

where: R can be equal to R ', Z can be equal to Z', R and R ¹ are aliphatic groups containing 1 to 8 carbon atoms, n, n ¹ and n "are numbers from 1 to 100, m is a number from 1 to 6 and Z and Z ¹ are selected from a large group of halogen complexing functional chemical constituents that prevent crystallization of the complex at 30 ° C, and X is an oxygen atom, HC-OR "or R ¹ " - C-OR ¹¹ , where R "and R ¹ " are aliphatic groups from 1 to

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Contains 6 carbon atoms. In addition, Z and Z ^{1 can} be chosen to increase the amount of halogen trapped in the complex or to increase its chemical stability. These functional groups include, but are not limited to: neutral groups such as alkyls, amides, carbocycles, esters, halocarbons, halides, hydrogen, hydroxyls, nitriles, phosphonate esters, pyridyls, siloxanes, sulfonate esters, sulfones, sultones, and tertiary amines; amphoteric groups such as amidimidines, betaines, phosphobetaines, sulfobetaines and amine oxides; mesoionic groups such as sydnones; anionic groups such as carboxylates, phosphonates and sulfonates; cationic groups such as ammonium, ammonium hydrohalide, phosphonium, pyridinium, quaternary ammonium, quaternary O-alkylhydroxylammonium and tertiary amine hydrohalide. Ammonium, ammonium hydrohalide, amididine, amine oxide, betaine, cyano, ester, hydroxyl, phosphobetaine, phosphonium, pyridinium, pyridyl, quaternary ammonium, quaternary O-alkyl, hydroxylammonium, sulfobetaine, sulfonium, sydnone and tertiary amine hydrohalide are not to be understood as limiting examples functional ingredients that create an additional halogen complex formation capacity.

If an ether additive having a cyclic structure is selected for the halogen complexing agent, it must be Ring have sufficient asymmetry to contribute to its respective halogen complexes from crystallizing 30 C. Cyclic ethers, such as N-substituted N-Methy1-morpholinium bromides, like that

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Ν, Ν-diethyl morpholinium bromide, which is used in US-PS 3 816 177 is described, form crystalline tribromides with melting points above 40 C and therefore do not include Embodiments of the present invention. Because of the The intrinsic crystallinity of the tribromides and the resulting viscosity are at temperatures below about 50 C. when compared with the complexes according to the invention, they are at least an order of magnitude less conductive. This leads to low discharge rates of N-substituted N-methyl-morpholinium tribromides below 50 ° C. Above 40 ° C, the chemical stability of the N-substituted N-methyl-nxorpholinium-perbromide becomes questionable what is shown by the slow formation of HBr.

Furthermore, Z can comprise non-functional components which are capable of irreversibly reacting with bromine. In this regard, Z should not include any phenyl or polycyclic aromatic groups, especially those Groups that are substituted with electron donating groups, such as alkyl or alkoxy, which are irreversible Greatly increase electrophilic bromination of aromatic rings. Other easily halogenatable molecules, such as ketones, olefins, acetylenes and aldehydes are also unsuitable. Accordingly, in the above-mentioned ZA patent described polyethers are not embodiments of the invention, since the alkyl-substituted PhenoRygruppe reacts with bromine as follows:

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- Wr-

Br + HBr

Ether according to the invention are when they are in voltaic ash Halogen cells and batteries are used to store bromine, advantageously because there is no further connection needs to be added, and because it is, as explained below, more effective complexes with halogens form as the two-part system described in US Pat. No. 3,816,177, which increases shelf life and the self-discharge of the cells is reduced, since the ether-bromine complexes of the compounds according to the invention remain fluid below 30 C, they can be discharged at low temperatures.

The mechanism by which halogens are believed to be complexed with these ethers is as given below Diagram (see E. Y. Gorenbein, N.O. Labkovskaya and I.L. Abarbarchuk, Zh. Obshch. Khim. 3 ^, 1921 (1965); CA 64: 6481a (1966) stated:

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or

where X is the halogen.

Thus, if the number of ether groups in a given compound is increased, the ability of the compound, Br ", Cl_, I ,. or to hold a polyhalide, increased. However, competing interactions and steric influences influence the complex formation and in in practice the ratio of the amount of complexed halogen to the number of ether groups present is non-linear.

Processes for the synthetic production of compounds of the type described above are generally known, cf., for example, Satkowski and Hsu, Polyoxyethylation of Alcohol , Industrial and Engineering Chemistry, Volume 49, p. 1875 (1957). The process described in this reference can be summarized as follows:

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Δ Δ

Z-OH - ► Z-O

(KOH) (KOH)

Δ Z - 0 <· ^ \ ^ 0 * ^ \ ^ - OH ► 2 - 0 * ~ s ^ 0- "N ^ O

(KOH)

Another method of making these compounds involves functionalizing a bromo ether or bromine polyethers as described, for example, in US Pat. No. 2,049,463 (1936). That from this patent specification known methods can be summarized as follows:

Z + RX-R'-Br > - RX-R'-ZBr

Various known modifications can result in a wide variety of the types of connections described. One Alkylation of commercially available hydroxyethylamines can advantageously be used and functional components capable of forming halogen complexes and which are not Ether groups can be used. A successful connection was established as follows:

25% trimethylamine in Methanol (35.5'g) stirred and cooled to OC °,

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while 2-bromoethyl-ethyl ether (15.3 g) is added dropwise is added. The reaction mixture is warmed to 25 ° C and stirred overnight. The methanol and the excess trimethylamine are removed under reduced pressure removed and the solid residue is crystallized from methanol / acetone, giving 18.4 g (84%) of a white crystalline Ether (ECO-2) results in the following reaction:

Me Br

CH ₃ CH 0 ^^^ Br + NMe ₃ fr »CH ₃ CH ₂ O ^ N ⁺ - Me

Me

ECO-2

Water-soluble dipolar additives, such as tetramethylene sulfone (SuIf ο lan), endeavor to reduce the halogen content of the ethers. Water-insoluble additives such as halogenated hydrocarbons (methylene chloride) also slightly reduce the halogen holding capacity of the ethers.

Fig. 1 shows a cell 10, which has a housing 12, two graphite electrodes 14, 16, a graphite felt mass 18 and a porous polymeric separator 20. The graphite electrode 14 serves as the bromine electrode; electrode 16 serves as the zinc electrode. Electrical supply lines (not shown) are connected to the electrode by clips. The electrodes 14, 16 have a porosity

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of 26X . Suitable graphite felt is commercially available from Union Carbide Corporation (VWF grade). A suitable separator is supplied by WR Grace, Inc. under the trade name DARAMIC.

Fig. 4 shows a bipolar, multi-cell battery 37 of the type in which the additive according to the invention is used. It has a waterproof glass case 39, which encloses two graphite plate current collectors 41, 43, The plate 43 serves as a metal electrode. Between the current collectors 41, 43 an arrangement of graphite felt masses 45 is provided, which serve as counter electrodes. A porous polymeric release liner 47 (Deramic, approximately 3.1 mm thick) and a bipolar electrode 49 (conductive polymer film made by Conductive Polymer Corporation, Marblehead, Massachusetts and has a thickness of about 0.5 mm) are in turn arranged between a graphite felt mass 45. The number the cells of the battery can of course be increased or decreased as needed.

The electrolyte of the electrochemical system described above, which is contained in the felt masses, comprises aqueous solutions of inorganic salts, such as zinc halide or cadmium halide, up to 50% of one or more of the compounds described above and can be 0 to 30 % of one or more contain various, known additives to improve application.

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To illustrate the effect of the compounds According to the invention, a cell was charged with a stationary electrolyte as described above until more than 80% of the initial amount was in solution existing zinc halides were converted to zinc and halogen. The charging current densities were typically

2 in a range from about 53.8 to about 269.1 A / m.

All cells were tested with constant current draw for various current densities.

Data obtained from these tests are summarized in FIG. The curves were obtained by measuring the current output in ampere-hours at various voltages for cells with a stationary electrolyte which had been charged in the manner described above. For the curve labeled A, the electrolyte consisted of 0.4M ZnBr ~ and 0.2M ZnSO in water. For curve B, the electrolyte consisted of 0.4M ZnBr ₂ , 0.2M ZnSO, and 7% by volume BL-330, an aliphatic polyether sold by GAF Corporation. The electrolyte of curve C consisted of 0.4M ZnBr ₂ , 0.2M ZnSO, and 0.4M (CH ₃ ) NBr in a volume ratio of 9: 1 of water to propylene carbonate. The electrolyte of curve D consisted of 0.4M ZnBr ₂ , 0.2M ZnSO ₄ and 5% by volume of NN'-bis-ethoxyethylene-N ^ jN'jN'-tetramethyl-2,2-bis-ethyleneoxydiammonium dibromide (ECO- 3). These curves show that a considerably larger number of ampere hours can be achieved in a cell whose electrolyte contains an ether compound according to the invention, and that the ether compounds, if they are added to the electro-

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lytes are added, with or without other halogen complex-forming substances that increase cell capacity.

Fig. 3 shows a cell 21 in which a circulating electrolyte is used which contains a halogen complex-forming additive according to the invention. Cell 21 has a housing 22, two graphite electrodes 23, 24, a graphite felt compound 25 and a porous, polymeric separator 26. The arrangement for storing the halogen complex 27 and for providing fresh electrolyte contains a pump 28, an electrolyte tank 29, a halogen complex tank 30 and two taps 31 and 32 for storage and releasing the halogen complex 27. During charging via clamps (not shown) attached to the electrodes 23 and 24, the halogen complex 27 in the Felt 25 formed from either a water soluble or a water insoluble ether additive in accordance with the invention; H. released Br _ unites in the above given way to a Br_-ether complex. The resulting insoluble halogen complex 27 is added to the tank pumped, where it can be drained back into the felt 25 by opening the tap 31 to during the unloading to be consumed. The metal is applied to the electrode 23 during charging, the quality of the application and the application characteristics, inter alia. from the flow velocity are dependent. If a water-insoluble ether additive 33 is used, can a storage tank 34 and two taps 35 and 36 for storage and

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Release of the ether additive 33 must be present. The electrolyte of the cell includes inorganic salts such as Zinc halide or cadmium halide, up to 50% of one or more of the compounds according to the invention and can contain 0 to 30% of one or more known additives to improve the application and coating parameters. It can be seen that complex 27 is being used can be used to operate cells other than those shown in FIG. For example are the complexes, except in zinc and cadmium cells, in other cells are useful in which halogen is used and which, for example, titanium, chromium or hydrogen as can have an anode.

To illustrate the effect of the compounds according to the invention, a cell with a circulating electrolyte was used of the type described above, ECO-I (cf. the structural formula given below) with current densities in one range

ο
charged from 107.6 to 645.8 A / m for periods of 1 to 3 hours. The cell was tested at a constant current draw for various current densities and was found to have a coulombic efficiency of 50 to 80% and an energy efficiency of 40 to 60%. Without an ether additive according to the invention, no halogen complex 27 is formed and the bromine which dissolves in the electrolyte reacts with the zinc plate on the electrode 23, which leads to a coulomb and energy efficiency of less than 5%.

The following table shows that the halogen complex formation

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property applies to a representative cross section of the class of compounds according to the invention. The data in this table was obtained by mixing the indicated amount of bromine in two flasks, the first flask containing 5 ml of 2M ZnBr ₂ and the second flask containing 5 ml of 4M ZnBr _2. The distribution of the bromine complex and the aqueous phase was achieved by vigorous stirring for 1/2 hour at 25 ° C. It has been shown that stirring for 18 hours under these conditions gave the same results. The bromine complex and the aqueous phases were then separated by centrifugation and the aqueous phase was titrated for bromine.

The table shows that the ether compounds according to the invention (Examples 3 and 6-12) have a larger Percentage of bromine available as liquids coraplex as either a quaternary ammonium salt of Example 1 or the system of quaternary ammonium salt and proton-free dipole (sulfolane) of Examples 2 and 5.

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Table 1 mM Br « % Br ₂ that in 5 ml waterier Distribute phase Complexation compound with: manure 2M ZnBr ₂ 4M ZnBr ₂ 16.4 (3 U) ⁺ 16% 16.4 26% 18% 1) QmBr * (3.28 mM) 16.4 12% 8th% 2) QtnBr * (3.28 mM)
Sulfolane (400 mg) 9.84 (li%) ⁺ (6%) * 3) QmBr * (3.28 mM)
GAF BL-330 (400 mg) 9.84 13% 9% 4) QmBr * (3.28 mM) 9.84 10% 8th% 5) QmBr * (3.28 (nM)
Suifulane (400 mg) 9.84 14% 11% 6) ECO-I (3.28 mM) 9.84 12% 9% 7) ECO-I (3.28 inM)
Sulfolane (400 mg) 9.84
9.84 14%
7% 12%
5% 8) ECO-2 (3.28 mM) 9.84 9% 6% 9) ECO-2 (3.28 uM)
Sulfoians (400 u \ g)
10) ECO-3 (3.28 mM) 9.84 8th% 5% ti) ECO-3 (3.28 mM)
Sulfolane (400 mg) 12) ECO-4 (3.28 mM)

* QmBr is phenyltrimethylammonium bromide sulfolane 1st tetramethylene sulfone GAF BL-330 is an aliphatic polyether from GAF

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. ar

Corporation

+ The quaternary airanonium polybromide phase was crystalline

ECO-L is ECO-2 1st

Br

Br

ECO-J lsi ECO-4 is

Bc

2Br

ECO-1 Ethoxyethylene-N, N * d imethy1-N-ethylammonium bromide ECO-2 ethoxyethylene-N, N, N-trimethylammonium bromide

ECO-3 N, N ^l -bis-ethoxyethylene-N, N, N ' _t N ^l -tetramethyl-2,2-bisäthylenoxydiammonlumdibromid

ECO-4 Ethoxyethylene-N, N, N-triethylammonium bromide

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Claims (23)

PATENT CLAIMS: . Method for improving the performance of Electrochemical systems delivering electricity, in which a substance is selected from the group which consists of TCrom, chlorine, iodine, polyhalogen complexes and mixtures thereof, as the electrochemically active one Agent is used, characterized in that an ether additive is added to the electrolyte of the system, which as an insoluble liquid in aqueous metal halide solutions at 30 C in the presence of a or several molar equivalents of halogen per ether oxygen is present in the ether and is selected from the group consisting of compounds having the following formula consists: b) 2 (-RXR ^) _n ² '; c) Z '(- RXR ^l -) _n Z (-Rx-R »-) _n , z (-RXR ^t ) _n ·· ² '; d) ZK-RXR ^) _n ²¹ J _1n ; and a) 2l 709838/094 7 ORIGINAL INSPECTED where: R can be equal to R ', Z can be equal to Z ¹ , R and R' are aliphatic groups containing 1 to 8 carbon atoms, n, n * and n "are numbers from 1 to 100, m is a number from 1 to 6, 7 and Z ¹ are chemical groups which make the ilalogene complex of the additive not crystalline at 30 C and the 7ii are incapable of substantially irreversible association with bromine, chlorine, or iodine, and X is selected from the group consisting of an oxygen atom, HC-OR ' ¹ , R''' - C-OR ", and combinations thereof, where R "and R ¹ " are aliphatic groups containing 1 to carbon atoms. 2. The method according to claim 1, characterized in that Z and Z ¹ are selected from the group consisting of alkylene, amides, carbocycles, carboxylates, halocarbons. Halides, hydrogen, phosphonates, siloxanes, sulfonates, sulfones, sultones, and combinations thereof. 3. The method according to claim 1, characterized in that Z and Z ¹ are selected from the group consisting of the functional constituents forming the halogen complexes. 709838/094 7 771169A 4. The method according to claim 3, characterized in that Z and Z ¹ are selected from the group consisting of ammonium, Atrnnoni.umhydrohalogeniden, amidimidines, amine Oxides, betaines, esters, hydroxyls, nitriles, phosphobetaines, Phosphoniums, Pyridinlums, Pyridylenes, quaternary ammonium, quaternary 0-alkyl-hydroxy! ammonium, Sulfobetaines, sulfoniums, sydnones, tertiary amines, tertiary amine hydrohalides and combinations the same exists. 5. The method according to claim 1, characterized in that the additive is an ether selected from the group is made up of: Ethoxylethylene-N, N, N-triethylammonium bromide; Äthoxyä thy len-NjN-dirnethyl-N -äthy lammoniumbromid; Ethoxyethylene-N, N, N-trimethylammonium bromide and N, N'-bis-ethoxyethylene-N, N, N ', N'-tetramethy1-2,2-bi s-ethylene oxide iammonium dibromide consists. 6. An electrochemical cell which operates according to the method according to any one of claims 1 to 5, characterized by a Housing, through a porous, conductive halogen electrode, an Me electrode, where Me is selected from the group which consists of zinc and cadmium, through an aqueous electrolyte, which is an inorganic salt of the formula MX where M is selected from the group consisting of cadmium and zinc, and where X is selected from the group is made up of bromide, chloride, iodide and combinations 709838/0947 functions of the same, and through an addition in the electrolyte, which comprises an ether compound which acts as an insoluble liquid in aqueous metal halide solutions at 30 C in the presence of one or more molar equivalents of halogen per ether oxygen in the additive is present, wherein the additive is an ether selected from the group consisting of compounds with the following formula consists: b) ZC-RXR ¹ -) _η ^Ζ 'ί C) Z ^l (-RXR ^l -) _n Z (-RXR »-) d) Z [(- R-X-R '-) "*']"; and ·> ^ where: R can be equal to R ¹ , Z can be equal to Z *, R and R 'are aliphatic groups containing 1 to 8 carbon atoms, n, n * and n "are numbers from 1 to 100, m is a number from 1 to 6, Z and Z ¹ are chemical groups which render the halogen complex of the additive non-crystalline at 30 C and which are incapable of substantially irreversible association with bromine, chlorine or iodine, and X is selected from the group consisting of an oxygen atom, HC-OR ", R ¹ " -C-OR ", and combinations thereof, where R" and R ¹¹ 'are aliphatic groups containing 1 to 1 carbon atoms. 709838/0947 r / 11694 7. A cell according to claim 6, characterized in that Z and Z ¹ are selected from the group consisting of alkylenes, amides, carbocycles, carboxylates, halocarbons, halides, hydrogen, phosphonates, siloxanes, sulfonates, sulfones, sultones, and combinations thereof . 8. Cell according to claim 6, characterized in that Z and Z ¹ are selected from the group consisting of functional components that form complexes with halogen, such as ammonium, ammonium hydrohalidone, amididines, amine oxides, betaines, esters, hydroxyls, nitriles, Phosphobetalnen, phosphoniums, pyridiniums, pyridylene, quaternary ammonium, quaternary 0-alkyl-hydroxylamnoniums, sulfobetaines, sulfoniums, sydnones, tertiary amines, tertiary amine hydrohalides and combinations thereof. 9. Cell according to claim 6, characterized in that the additive is a compound selected from the group is which of: Ethoxylethylene-N, N, N-triethylammonium bromide; Ethoxyethylene-N, N-methyl-N-äthylammoniumbrotnld; Ethoxyethylene-N, N, N-trimethylammonium bromide and N, N'-bis-ethoxyethylene-N, iJ, N ·, W -tetramethyl-2, 2-bi s-ethy1enoxide iammoniuradibromide consists. 709838 / 094V 10. Cell according to one of claims 6 to 9, characterized in that that the cell is a secondary cell 11. Cell according to one of claims 6 to 10, characterized by means for storing the during charging generated complex. 12. Cell according to one of claims 6 to 11, gekennzeinet by means for circulating the electrolyte. 13. Cell according to claim 12, characterized by means for storing the additive. 14. Water-insoluble, liquid complex which is essentially insoluble in water at 30 C for use in the electrochemical cells according to one of the claims
6 to 13, in which _e used i _n halogen, which is selected from the group, bromine, iodine, Polyhalogenkomplexen and mixtures of chlorine thereof, characterized in that the complex consists essentially of a substance from the Is selected from the group consisting of chlorine, bromine, iodine, polyhalogen complexes, and mixtures thereof, combined with an ether selected from the group consisting of compounds having the following formula: 709838/094 7 7711694 a) (RXR ¹ ) _m ² ; b) Z (-R-X-R * -) "*"; c) 2 ^l (-RXR ^l -) _n ^z (-RXR ^l -) _n .2 (-RXR ^l ) _n ^tlZl ; d) Zl (-RXR '.) _n ^z '] _a ; and e) Zl where: R can be equal to R ¹ , Z can be equal to Z *, R and R * are aliphatic groups containing 1 to 8 carbon atoms, n, n * and n "are numbers from 1 to 100, m is a number from 1 to 6, Z and Z 'are chemical groups which make the halogen complex of the additive not crystalline at 30 C and which are incapable of substantially irreversible combination with bromine, chlorine or iodine, and X is removed from the group consisting of an oxygen atom, HC-OR ", R"'- C-OR ", and combinations thereof, wherein R" and R ¹ "are aliphatic groups containing 1 to carbon atoms. 15. A complex according to claim 14, characterized in that Z and Z ¹ are selected from the group consisting of alkylenes, amides, carbocyls, carboxylates, halocarbons, halides, hydrogen, phosphonates, siloxanes, sulfonates, sulfones, sultones and combinations thereof . 7 0 9 8 3 8/0947 16. Complex according to claim 14, characterized in that Z and Z * are selected from the group consisting of with functional components that form halogen complexes consists. 17. Complex according to Ansoruch 14, characterized in that Z and Z ¹ are selected from the group consisting of ammonium, ammonium hydrohalides, amidiraidines, Arain oxides, betaines, esters, hydroxyls, nitriles, phosphobetaines, phosphonium, pyridinium, pyridylene, quaternary Ammonium, quaternary O-alkyl-hydroxylammoniums, sulfobetaines, sulfoniums, sydnones, tertiary amines, tertiary amine hydrohalides and combinations thereof. 18. Complex according to claim 14, characterized in that the ether is selected from the group consisting of: EthoxylMethylene-N, N, N-triethylammonium bromide; Ethoxyethylene-N, N-dimethyl-N-ethylamraonium bromide; Ethoxyethylene-N, N, N-trimethylammoniumbroraid and N, N'-bis-ethoxyethylene-N, N, H ', N ¹ -tetramethyl-2,2-bis-ethylene oxide, ammonium dibromide consists. 19. Battery that works according to the method according to one of claims 1 to 5, characterized by a housing, through a Me electrode, where Me is a metal made up of 0 9 8 3 8/0947 is selected from the group consisting of cadmium and zinc, by a plurality of counter electrodes spaced apart from the Me electrode, by a bipolar electrode disposed between each adjacent pair of Gepen electrodes, by an aqueous electrolyte that is an inorganic Containing salt of formula MX, where M is selected from the group consisting of cadmium and zinc, and where X is selected from the group consisting of broraixl, chloride, iodide, and combinations thereof, and by an additive in the electrolyte, ^ e ^ pine ether compounds which are present as an insoluble liquid in aqueous metal halide solutions at 30 C in the presence of one or more molar equivalents of the halogen per ether oxygen in the additive, the additive being selected from the group consisting of compounds having the following formula: b) Z (-RX-R'-) _n ^Zt; c) Z '(- RXR ^l -) _n ^z (-RXR ^l -) _n , 2 (-RXR ^l ) _n ^llZt ; d) Zl (-RXR ^) _n ²¹ I _n ; and β) MZJ 09838/0947 where: R can be equal to R ', Z can be equal to Z ¹
be, R and R 'are aliphatic groups from 1 to
Contains 8 carbon atoms, n, n 'and n "are numbers from 1 to 100, m is a number from 1 to 6, Z and Z'
are chemical groups that make the halogen complex of the additive not crystalline at 30 C and the 7ii
are incapable of substantially irreversible association with bromine, chlorine or iodine, and X is selected from the group consisting of an oxygen atom,
HC-OR ", R ¹ ^ -C-OR" and combinations thereof, where R "and R ^{'11 are} aliphatic groups containing 1 to 1 carbon atoms. 20. Battery according to claim 19, characterized in that Z and Z 'are selected from the group consisting of alkylene, Amides, carbocycles, carboxylates, halocarbons, halides, hydrogen, phosphonates, siloxanes, Sulfonates, sulfones, sultones, and combinations thereof consists. 21. Battery according to claim 19, characterized in that Z and Z ¹ are selected from the group consisting of functional constituents which form complexes with halogen, such as, for example Ammonium, ammonium hydrohalides, amidiraidines, amine oxides, Betaines, esters, hydroxyls, nitriles, phosphobetaines, phosphoniums, pyridiniums, pyridylenes, 09838/0947 ORIGINAL INSPECTED quaternary ammonium, quaternary 0-alkyl-hydroxylam moniums, sulfobetaines, sulfoniums, sydnones, tertiary amines, tertiary amine hydrohalides and combinations thereof. 22. Ratterte according to claim 19, characterized in that the additive is a compound selected from the group selected from: Ethoxylethylene-NjNjN-triethylammonium bromide; Ethoxyethylene-N, N-dimethyl-N-äthylammoniumbromidj Äthoxyäthylen-NjNjN-trimethylammoniumbromid and NtN'-bis-Äthoxyäthylen-N, !!, « ¹ , N ¹ -tetramethyl-2,2-bis -äthy lenoxid iatnmoniumdibromid consists. 23. Battery according to claim 19, characterized by means for storing the generated during charging Complex. 09838/0947